Binuclear N-heterocyclic N,N-diglycidyl compounds, processes for their manufacture and their use

ABSTRACT

WHEREIN R&#39;&#39;, R&#39;&#39;&#39;&#39;, R&#39;&#39;&#39;&#39;&#39;&#39; and R&#39;&#39;&#39;&#39;&#39;&#39;&#39;&#39; independently of one another each denotes a hydrogen atom or an alkyl radical having 1 to 4 carbon atoms or R&#39;&#39; and R&#39;&#39;&#39;&#39; represent together a pentamethylene radical, and n denotes the number 1 or 2. These compounds are resins which are viscous to solid at room temperature, and which can be converted with curing agents to products having good mechanical and electrical properties.   WHEREIN X1 and X2 each denotes a hydrogen atom or a methyl group, R1 and R2 each represents a hydrogen atom, a methyl group, an ethyl group or a phenyl group, X represents an aliphatic hydrocarbon radical having 1 to 14 carbon atoms, a cycloaliphatic hydrocarbon radical having 5 or 6 carbon atoms, an araliphatic hydrocarbon radical having 7 to 14 carbon atoms or an aromatic hydrocarbon radical having 6 to 14 carbon atoms, Z1 and Z2 are radicals of the formulae Binuclear N-heterocyclic N,N&#39;&#39;-diglycidyl compounds of the formula

United States Habermeier et a1.

atent r 1 BINUCLEAR N-HETEROCYCLIC N,N-DIGLYCIDYL COMPOUNDS, PROCESSESFOR THEIR MANUFACTURE AND THEIR USE [75] Inventors: Juergen Habermeier,Allschwil;

Dieter Baumann, Birsfelden; Daniel Porret, Binningen; Hans Batzer,Arlesheim, all of Switzerland [73] Assignee: Ciba-Geigy AG, Basle,Switzerland [22] Filed: Dec. 15, 1972 [21] Appl. No.: 315,396

Related US. Application Data [63] Continuation-in-part of Ser. No.144,407, May 17,

1971, abandoned.

[30] Foreign Application Priority Data May 22, 1970 Switzerland 7627/70[52] US. Cl..... 260/309.5, 117/124 E, 117/161 ZB, 161/185, 161/186,260/2 EP, 260/2 EA, 260/2 EC, 260/18 EP, 260/304 EP, 260/306 R, 260/318E, 260/37 EP, 260/47 EP,

260/59, 260/775 R, 260/784 EP, 260/80 P, 260/2564 C, 260/830 R, 260/830P, 260/830 S, 260/830 TN, 260/831, 260/834 [51] Int. Cl C07d 49/32 [58]Field of Search 260/3095, 256.4 C

[56] References Cited UNITED STATES PATENTS 3,391,097 7/1968 Williamson260/3095 3,542,803 11/1970 Porret 260/3095 3,629,263 12/1971 Batzer eta1 260/3095 3,640,910 2/1972 Porret et a1 260/3095 FOREIGN PATENTS ORAPPLICATIONS 2,125,355 12/1971 Germany 260/3095 Primary Examiner-NatalieTrousof Attorney, Agent, or Firnz-Vincent J. Cavalieri 1 1 Mar. 18, 1975wherein X, and X each denotes a hydrogen atom or a methyl group, R and Reach represents a hydrogen atom, a methyl group, an ethyl group or aphenyl group, X represents an aliphatic hydrocarbon radical having 1 to14 carbon atoms, a cycloaliphatic hydrocarbon radical having 5 or 6carbon atoms, an araliphatic hydrocarbon radical having 7 to 14 carbonatoms or an aromatic hydrocarbon radical having 6 to 14 carbon atoms, Zand 2 are radicals of the formulac R' C. or C \RII RIII wherein R, R, R'and R independently of one another each denotes a hydrogen atom or analkyl radical having 1 to 4 carbon atoms or R and R" represent togethera pentamethylene radical, and a denotes the number 1 or 2.

These compounds are resins which are viscous to solid at roomtemperature, and which can be converted with curing agents to productshaving good mechanical and electrical properties.

7 Claims, N0 Drawings wherein R, R", R and R" independently of oneanother each denotes a hydrogen atom or an alkyl radical having I to 4carbon atoms or R represent together a pentamethylene radical, and ndenotes the number I or 7 Preferred is a compound of formula (I).wherein X, is identical with X R is identical with R and 7., isidentical with Z and a compound of formula (I), wherein X represents analiphatic hydrocarbon radical wherein X and X each denote a hydrogenatom or a methyl group, R, and R each represent a hydrogen atom, amethyl group, an ethyl group or a phenyl group, Z and Z independently ofone another each denote a nitrogen-free divalent radical which isrequired to complete a five-membered or six-membered, unsubstituted orsubstituted heterocyclic ring, X represents the hydrocarbon radical of adicarboxylic acid obtained by removing the carboxyl groups, and ndenotes the number 1 or 2.

The radicals Z and Z in the formula (I) preferably consist only ofcarbon and hydrogen, or of carbon, hydrogen and oxygen. They can, forexample, be radicals of the formulae wherein R, R", R and R""independently of one another each can denote a hydrogen atom or, forexample, an alkyl radical, an alkenyl radical, a cycloalkyl radical oran optionally substituted phenyl radical.

Especially, the present invention relates to a com pound of the formula(I), wherein X and X each denotes a hydrogen atom or a methyl group, Rand R represents a hydrogen atom, a methyl group, an ethyl group or aphenyl group, X represents an aliphatic hydrocarbon radical having 1 to14 carbon atoms, a cycloaliphatic hydrocarbon radical having 5 to 6carbon atoms, an araliphatic hydrocarbon radical having 7 to 14 carbonatoms or an aromatic hydrocarbon radical having 6 to 14 carbon atoms, Zand Z are radicals of the formulae having 2 to 8 carbon atoms, acyclohexylene radical or a phenylene radical.

The new N,N'-diglycidyl compounds of the formula (I) are, as a rule,resins which are viscous to solid room temperature, and which can beconverted with customa-ry curing agents for epoxide resins, such asdicarboxylic anhydrides or polyamines, either as they are or- RIIIIproducts described in the above cited patent specifica' tions are lowerthan those of the cured products according to the present invention.

The products described in the U.S. Pat. No. 3,391,097 are modified byunsaturated fatty acids, whereby the epoxide groups are destroyed by theaddition reaction of the carbon acids. The products are cured'by actingof air on the olefmic groups in the compounds. These compounds aretherefore quite different from those defined herein and would not renderthe products according to the present invention obvious to an expert.

The new diepoxides of the formula (l) are manufactured according tomethods which are in themselves known. A preferred process according tothe invention /R' R for their manufacture is characterised in that, in acomor pound of the formula \RH i \R" I C=0 H 0 O H O=C "Z I I [I ii I lY-CH -N N-Cl-l -C-O-C lXiC-O-C-Cll -N N-Cll, -Y' (II) n l I 2 2 C C 8 12 (l wherein R R Z Z, X, and n have the same meaning as in the formula(I) and the radicals Y and Y are radicals which can be converted into1,2-epoxyethyl radicals or l-methyl-l ,2-epoxyethyl radicals, Y and Yare converted into epoxyethyl or l-methyl-l,2-epoxyethyl radicals.

A radical Y or Y which can be converted into the l,2-epoxyethyl radicalor l-methyl-l ,2-epoxyethyl radical is above all a hydroxyhalogenoethylradical which carries the functional groups on different carbon atoms,especially a 2-halogeno-l-hydroxyethyl radical or a2-halogeno-l-hydroxy-l-methylethyl radical. Halogen atoms are hereespecially chlorine or bromine atoms. The reaction takes place in theusual manner, above all in the presence of agents which split offhydrogen halide, such as strong alkalis, for example anhydrous sodiumhydroxide or aqueous sodium hydroxide solution. It is, however, alsopossible to employ other strongly alkaline reagents, such as potassiumhydroxide, barium hydroxide, calcium hydroxide, sodium carbonate orpotassium carbonate.

A further radical Y or Y which can be converted to the l,2-epoxyethylradical is, for example, the ethenyl radical, which can be convertedinto the 1,2- epoxyethyl radical in a known manner, such as, above all,by reaction with hydrogen peroxide or per-acids, for example peraceticacid, perbenzoic acid or monoperphthalic acid.

The starting substances of the formula (II) are obtained in a mannerwhich is in itself known. Thus it is, for example, possible to react adiester of the formula (III) wherein R R Z Z X and n have theabovementioned meaning, with a compound of the formula YCH I-Ial,wherein Hal represents a halogen atom and Y has the abovementionedmeaning. Preferably, the compound of the formula (III) is reacted withan epihalogenohydrin or B-methylepihalogenohydrin, above allepichlorohydrin or B-methylepichlorohydrin, in the presence of acatalyst, such as, especially, a tertiary amine, a quaternary ammoniumbase or a quaternary ammonium salt. Suitable catalysts for the additionof epichlorohydrin or ,B-methylepichlorohydrin are above all tertiaryamines, such as triethylamine, tri-npropylamine, benzyldimethylamine,N,N- dimethylaniline and triethanolamine; quaternary ammonium bases,such as benzyltrimethylammonium hydroxide; quaternary ammonium salts,such as tetramethylammonium chloride, tetraethylammonium chloride,benzyltrimethylammonium chloride, benzyltrimethylammonium acetate andmethyltriethylammonium chloride; hydrazines having a tertiary nitrogenatom, such as l,l-dimethylhydrazine, which can also be employed in thequaternised form; alkali halides, such as lithium chloride, potassiumchloride, sodium chloride, sodium bromide or sodium fluoride; also, ionexchange resins having tertiary or quaternary amino groups, as well asion exchangers having acid amide groups. Basic impurities, which canoccur in technical commercially available forms of the startingcompounds, can also act as catalysts. In such cases it is not necessaryto add a special catalyst.

The manufacture of the intermediate products of the formula (II) and ofthe end products of the formula (III) is appropriately carried out in asingle two-stage process, without isolation of the intermediate products(II).

A preferred embodiment of the process therefore consists, for example,or reacting an epihalogenohydrin or fi-methyl-epihalogenohydrin,preferably epichloro hydrin or B-methylepichlorohydrin, with a diesterof the formula (III) in the presence of a catalyst, such as, preferably,a tertiary amine, a quaternary ammonium base or a quaternary ammoniumsalt, and in a second stage treating the resulting product containinghalogenohydrin groups with agents which split off hydrogen halide. Inthese reactions, the procedure described above is followed, and it ispossible to use the abovementioned compounds as catalysts for theaddition of epihalogenohydrin or ,B-methylepihalogenohydrin and- /or forthe dehydrohalogenation. Particularly good yields are obtained if anexcess of epichlorohydrin or B-methylepichlorohydrin is used. A partialepoxidisation of dichlorohydrin or of the dichloro-B- methylhydrin ofthe diester (III) already occurs during the first reaction, before theaddition of alkali. The epichlorohydrin or the B-methylepichlorohydrin,which act as hydrogen chloride acceptors, have then been partiallyconverted into glyceroldichlorohydrin or into,8-methylglycerol-dichlorohydrin.

The symmetrical diesters of the formula (III) can be manufacturedaccording to known methods, by esterification of 1 mol of diearboxylicacid of the formula 0 9 i ii HO-C- [X l -COH n l with 2 mols ofaN-heterocyclic monoalcohol of the formula Diesters of the formula (III)which are of unsymmetrical structure can, for example, be obtained byfirst partially esterifying l mol of a dicarboxylic acid (IV) with 1 molof a monoalcohol of the formula (Va) and in a second stage manufacturingthe diester with 1 mol of monoalcohol (Vb) which is different from themonoalcohol (Va).

Possible dicarboxylic acids of the formula (IV) are those of thealiphatic, cycloaliphatic, araliphatic and aromatic series. Thefollowing may be mentioned: oxalic acid, malonic acid, succinic acid,glutaric acid, adipic acid, pimclic acid, suberic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxy- G g g (VIb) with 1mol of monoepoxide of the formula 1 2 (VIIa) 'or 2' 2 (VIIb) O first, inthe presence of a suitable catalyst, Z or Z and R or R having the samemeaning as in the formula (I).

Suitable monoepoxides of the formulae (Vlla) or (Vlllb) are ethene oxide(ethylene oxide), propene oxide (propylene oxide), l,2butene oxide andstyrene oxide.

Since the endocyclic NHgroup located between two carbonyl groups is morestrongly acid, it reacts preferentially with the monoepoxide, so that ifonly a slight excess of the monoepoxide over the stoichiometric amountrequired to form a monoalcohol is employed, the monoalcohol of theformula (Va) or (Vb) is produced practically quantitatively.

The addition of the monoepoxide to the more strongly acid NHgroup of theN-heterocyclic compound can be effected in the presence of either acidor alkaline catalysts.

Preferably, however, alkaline catalysts, such as tetraethylammoniumchloride or tertiary amines, are used in the manufacture of themonoalcohols. However, alkali halides, such as lithium chloride orsodium chloride, can also be employed successfully for this additionreaction; it also takes place without catalysts.

The mononuelear N-heterocyclic compounds of the formulae (Vla) or (Vlb)used for the manufacture of the monoalcohols of the formulae (Va) or(Vb) respectively are above all hydantoin, hydantoin derivatives,barbituric acid, barbituric acid derivatives, uracil, uracilderivatives, dehydrouracil and dihydrouraeil derivatives, and alsoparabanic acid.

Hydantoin and its preferred derivatives correspond to the generalformula 1 (VIII) wherein R and R together form a tetramethylene orpentamethylene radical. Hydantoin, S-methylhydantoin,S-methyl-S-ethylhydantoin, -npropylhydantoin, 5-isopropyl-hydantoin,1,3-diazaspiro-(4.5 )-decane-2,4 dione, nonane-2,4-dione andl,3-diaza-spiro(4.4 preferably 5,5-dimethylhydantoin may be mentioned.

Barbituric acid and its preferred derivatives correspond to the generalformula 0 ll '0 2 EN NH. l l R-C6 4C= l Y on 6 wherein R and R bothdenote hydrogen, or one of the two radicals denotes a hydrogen atom andthe other radical denotes a methyl group,

Uracils of the formula (X) are uracil itself, and also 6-methyl-uraciland thymin S-methyl-uracil).

Dihydrouracil 2,4 dioxo-hexahydropyrimidine) and its preferredderivatives correspond to the general formula:

wherein R and R both denote a hydrogen atom or identical or differentalkyl radicals, preferably alkyl radicals with l to 4 carbon atoms, andR and R independently of one another each denote a hydrogen atom or analkyl radical.

Preferably, the two radicals R and R in the above formula denote methylgroups, R denotes a hydrogen atom or a lower alkyl radical with l to 4carbon atoms, and R denotes a hydrogen atom. The following may bementioned: 5,6-dihydrouracil, 5,5-dimethyl-5,6- dihydrouracil(2,4-dioxo-5,S-dimethylhexahydropyrimidine) and5,5-dimethyl-6-isopropyl-5,6-

dihydrouracil (2,4-dioxo-5,5-dimethyl-6-isopropylhexahydropyrimidine).

The new N,N'-diglycidyl compounds of the formula (1), according to theinvention, react with the customary curing agents for polyepoxidecompounds and can therefore be cross-linked or cured by the addition ofsuch curing agents, analogously to other polyfunctional epoxidecompounds or epoxide resins. Basic or acid compounds can be used as suchcuring agents.

As suitable curing agents there may be mentioned, for example: amines oramides, such as aliphatic, cycloaliphatic or aromatic, primary,secondary and tertiary amines, for example monoethanolamine,ethylenediamine, hexamethylenediamine, trimethylhexamethylenediamine,diethylenetriamine, triethylenetetramine, tetraethylenepentamine,N,N-dimethylpropylenediamine-l,3, N,N-diethylpropylenediaminel,3,bis(4-amino-3-methyl-cyclohexyl)methane, 3,5,5-trimethyl-B-(aminomethyl)cyclohexylamine (isophoronediamine), Mannichbases, such as 2,4,6- tris(dimethylaminomethyl)phenol;mphenylenediamine, p-phenylenediamine, bis(4- aminophenyl)methane,'bis(4-aminophenyl)sulphone, m-xyxylendeiamine;N-(2-aminoethyl)-piperazine; adducts of acrylonitrile or monoepoxides,such as ethylene oxide or propylene oxide, to polyalkylenepolyamines,such as diethylenetriamine or triethylenetetramine; adducts ofpolyamines, such as diethylenetriamine or triethylenetetramine, inexcess, and polyepoxides, such as diomethane-polyglycidyl ethers;ketimines, for example from acetone or methyl ethyl ketone andbis(p-aminophenyl)methane; adducts of monophenols or polyphenols andpolyamines; polyamides, especially those from aliphatic polyamines, suchas diethylenetriamine or triethylenetetramine and dimerised ortrimerised unsaturated fatty acids, such as dimerised linseed oil fattyacid (VERSAMID); polymeric polysulphides (THlOKOL); dicyandimide,aniline-formaldehyde resins; polyhydric phenols, for

example resorcinol, 2,2-bis(4-hydroxyphenyl)propane orphenolformaldehyde resins; boron trifluoride and its complexes withorganic compounds, such as BF -ether complexes and BP -amine complexes,for example BF monoethylamine complex; acetoacetanilide-BF complex;phosphoric acid, triphenylphosphite, polybasic carboxylic acids andtheir anhydrides, for example phthalic anhydride, N-tetrahydrophthalicanhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalieanhydride, 3,6-endomethylene-N-tetrahydrophthalic anhydride,methyl-3,6-endomethylene-A -tetrahydrophthalic anhydride methylnadicanhydride), 3,4,5,6,7,7-hexachloro-3,o-endomethylene-A-tetrahydrophthalic anhydride, succinic anhydride, adipic anhydride,azelaic anhydride, sebacic anhydride, maleic anhydride,dodecenylsuceinic anhydride; pyromellitic dianhydride or mixtures ofsuch anhydrides.

Cure accelerators can furthermore be employed in the curing reaction;when using polyamides, dicyandiamide, polymeric polysulphides orpolycarboxylic anhydrides as curing agents, suitable accelerators are,for example, tertiary amines, their salts or quaternary ammoniumcompounds, for example 2,4,6-tris(dimcthylaminomethyl)phenol,benzyldimethylamine. 2-ethyl-4-methyl-imidazole, 4-amino-pyridine,triamylammonium phenolate, and also alkali metal alcoholates, such as,for example, sodium hcxanetriolatc. Monophenols or polyphenols, such asphenol or diomethane, salicyclic acid or thiocyanates can, for example,be employed as accelerators when curing with amines.

The term curing", as used here, denotes the conver sion of theabovementioned diepoxides into insoluble and infusible, cross-linkedproducts, and as a rule, in particular, with simultaneous shaping togive mould ings, such as castings, pressings or laminates and the like,or to give sheet-like strucures", such as coatings, coverings, lacquerfilms or adhesive bonds.

Depending on the choice of the curing agent, the curing can be effectedat room temperature (l824C) or at elevated temperature (for example 50-lC).

The curing can, if desired. also be carried out in 2 stages, by firstprematurely stopping the curing reac tion, or carrying out the firststage at only a moderately elevated temperature, whereby a curableprecondensate which is still fusible and soluble (a so-called B- stage)is obtained from the epoxide component and the curing agent component.Such a precondensate can, for example, serve for the manufacture ofprepregs, compression moulding compositions or sintering powders.

The new N,N'-diglycidyl compounds can also be used as a mixture withother curable diepoxide or polyepoxide compounds. As such, the followingmay, for example, be mentioned: polyglycidyl ethers of polyhydricalcohols, such as 1,4-butanediol, A cyclohexenedimethanol, polyethyleneglycols, polypropylene glycols, 1,3-di-(2 '-hydroxy-n-propyl )-5 ,5-dimethylhydantoin or 2,2-bis-(4'-hydroxycyclohexyl)- propane;polyglycidyl ethers of polyhydric phenols, such as2,2-bis-(4'-hydroxyphenyl)-propane diome thane),2,2-bis-(4'-hydroxy-3,S'-dibromo-phenyl)- propane,bis-(4-hydroxyphenyl)-sulphone, l ,l ,2,2-tetrakis(4-hydroxyphenyl)ethane or condensation products, manufacturedin an acid medium of formaldehyde with phenols, such phenol novolacs orcresol novolacs; polyglycidyl esters of polycarboxylic acids, such as,for example, phthalic acid diglycidyl ester, isophthalic acid diglycidylester, tetrahydrophthalic acid diglycidyl ester or hexahydrophthalicacid diglycidyl ester; triglycidyl isocyanurate, N,N'-diglycidyl-5,5-dimethylhydantoin, 3-(2'-hydroxy-n-propyl)-5,5- dimethylhydantoin,aminopolyepoxides such as are obtained by dehydrohalogenation of thereaction products of epihalogenohydrin and primary or secondary amines,such as aniline or 4,4- diaminodiphenylmethane'. further, alieycliccompounds containing several epoxide groups, such as vinylcyclohexenediepoxide, dicyclopentadiene diepoxide, ethylene glycol-bis-(3,4-epoxytetrahydrodicyclopentadien-8-yl)-ether, (3,4-epoxycyclohexylmethyl)-3,4-epoxycyclohexanecarboxylate, (3'4'-epoxy-6'-methylcyclohexylmethyl3,4-epoxy-6-methylcyclohexanecarboxylate. bis-(2,3-

epoxycyclopenty1)-ether or 3-(3,4'-epoxycyclohexyl)-2,4-dioxa-spiro-(5,5)-9,l-epoxyundecane. If desired, other knownreactive diluents, such as, for example, styrene oxide,butyl-glycidyl-ether, diglycidyl-formal, isooctyl-glycidyl-ether,phenyl-glycidyl-ether, cresylglycidyl-ether, and glycidyl esters ofsynthetic, highly branched, mainly tertiary aliphatic monocarboxylicacids (CARDURA E) can also be used conjointly.

A further subject of the present invention are therefore curablemistures which are suitable for the manufacture of mouldings, includingsheet-like structures, and which contain the N,N'-diglycidyl compoundsof the formula (1), according to the invention, optionally together withother diepoxide or polyepoxide compounds and also curing agents forepoxide resins, such as polyamines or polycarboxylic anhydrides.

The diepoxides according to the invention, or their mixtures with otherpolyepoxide compounds and/or curing agents, can furthermore be mixed, inany stage before curing, with customary modifiers, such as extenders,fillers and reinforcing agents, pigments, dystuffs, organic solvents,plasticisers, flow control agents, agents for conferring thixotropy,flame-proofing sub stances and mould release agents.

As extenders, reinforcing agents, fillers and pigments which can beemployed in the curable mixtures accord ing to the invention, there may,for example, be mentioned: coal tar, bitumen, textile fibres, glassfibres, asbestos fibres, boron fibres, carbon fibers, cellulose,polyethylene powder and polypropylene powder; quartz powder; mineralsilicates, such as mica, asbestos powder and slate powder; kaolin,aluminium oxide trihydrate, chalk powder, gypsum, antimony trioxide,bentones, silica acrogel (AEROSIL), lithopones, barytes, titaniumdioxide, carbon black, graphite, oxide pigments, such as iron oxide, ormetal powders, such as aluminum powder or iron powder.

Suitable organic solvents for modifying the curable mixtures are, forexample, toluene, xylene, n-propanol, butyl acetate, acetone, methylethyl ketone, diacetonealcohol, ethylene glycol monomethyl ether,monoethyl ether and monobutyl ether.

Examples of plasticisers which can be employed for modifying the curablemixtures are dibutyl phthalate, dioctyl phtalate and dinonylphthalate,tricresyl phosphate, trixylenyl phosphate and polypropylene glycols.

Silicones, cellulose acetobutyrate, polyvinyl butyral, waxes, stearatesand the like (which in part are also used as mould release agents) can,for example, be added as flow control agents for employing the curablemixtures, especially in surface protection.

Particularly for use in the lacquer field, the diepoxide compounds canfurther more be partially esterified in a known manner with carboxylicacids, such as, especially, higher unsaturated fatty acids. It isfurthermore possible to add other curable synthetic resins, for examplephenoplasts or aminoplasts, to such lacquer resin formulations.

The manufacture of the curable mixtures according to the invention canbe effected in the usual manner with the aid of known mixing equipment(stirrers, kneaders, rolls and the like).

The curable epoxide resin mixtures according to the invention are aboveall employed in the fields of surface protection, the electricalindustry, laminating processes and the building industry. They can beemployed in a formulation adapted in each case to the special end use,in the unfilled or filled state, optionally in the form of solutions oremulsions, as paints, lacquers, compression moulding compositions,sintering powders, dip ping resins, casting resins, injection mouldingformulations, impregnating resins and binders, adhesives, tool resins,laminating resins, sealing and filling compositions, floor coveringcompositions and binders for mineral aggregates.

In the Examples which follow, unless otherwise stated, parts denoteparts by weight and percentages denote percentages by weight. Therelationship of parts by volume to parts by weight is as of themillilitre to the gram.

To determine the mechanical and electrical properties of the curablemixtures described in the Examples which follow, sheets of 92 X 41 X 12mm were manufactured for determining the flexural strength, deflection,impact strength and water absorption. The test specimens (60 X 10 X 4mm) for determining the water absorption and for the flexural test andimpact test (VSM 77,103 and VSM 77,105, respectively) were ma chinedfrom the sheets.

Test specimens of sizes 120 X 15 X 10 mm were in each case cast fordetermining the heat distortion point according to Martens (DIN 53,458).

Sheets of sizes 120 X 120 X 4 mm were cast for testing the arcingresistance and the tracking resistance (VDE 0303).

MANUFACTURE OF THE STARTING SUBSTANCES.

A. Monoalcohols 1. Manufacture of dimethylhydantoin.

a. 896 g of 5,5-dimethylhydantoin (7 mols) and 5.92 g of lithiumchloride in 900 ml of dimethylformamide are stirred at 50C. 458 g ofpropene oxide (7.7 mols) are added dropwise over the course of one hour,with gentle stirring. After the addition, the mixture is stirred for 3hours at 55C. The heating bath is then brought to 100C. The reaction isslightly exothermic, and the contents of the flask rise to 112C. After 1hour, the exothermic effect has subsided and the reaction is hencecomplete. The solution is filtered. After having been cooled to roomtemperature, the batch is adjusted to pH 7 with about 15 ml of 20%strength sulphuric acid. The dimethylformamide is recovered bydistilling off under a waterpump vacuum, and the product is subsequentlyisolated by drying at 95C under 0.1 mm Hg. 1305 g of aneggshell-coloured crystal mass of theory) are obtained. The product canbe purified by recrystallisation from acetone. A colourless, crystallineproduct of melting point 8384.5C is obtained, in approximately 80% yieldof pure material.

Elementary analysis shows the following:

3-( 2-hydroxy-n-propy )-5 ,5-

Found'. Calculated:

14.93% N 15.04% N 7.59% H 7.58% H ill The proton resonance spectrum (60Mc H-NMR, re-v corded in CDCl at 35C, with tetramethylsilane as theinternal standard) furthermore shows, through the presence of thefollowing signals, that the structure given below applies to the newcompound:

3 protons:

= 1,17 and 1,17 and 1.28 (doublet):

6 protons: 1.50 (singlet):

4 protons: 5.55 and 3.65 (doublet):

Found: Calculated:

and .04.2 (multiplet): -Ei] l proton: 7.15

Theoretical number of protons: 14

The structure is, accordingly b. A mixture of 256 g. of5,5-dimethylhydantoin, 159 g of potassium carbonate, 208 g of1-chloro-2- hydroxypropane (propylene chlorohydrin) and 500 ml ofdimethylformamide is stirred for 3 hours at 120C. A vigorous stream ofCO is evolved. Thereafter the mixture is stirred for a further 3 hoursat 130C. The batch is cooled to room temperature, the inorganic materialis filtered off, and the substance is isolated by dis tillingoff thedimethylformamide under a waterpump vacuum. 240 g of a colourlesscrystal mass (corresponding to 65% of theory) are obtained.

The product can be purified by recrystallisation from acetone. Analysesand spectra show that the product is identical with the preparationmanufactured according to instruction (A) (1) (a). 2. Manufacture ofdimethylhydantoin.

A solution of 529 g of ethylene oxide (12 mols) in 750 ml ofdimethylformamide is added to a solution of 1281 g of5,5-dimethylhydantoin mols) and 20 g of lithium chloride in 1200 ml ofdimethylformamide at C. This mixture is warmed to 4550C over the courseof 1 hour, and stirred at about 50C for 2 hours.

Thereafter the temperature is further raised to 60C for hours. Aftercompletion of the reaction the mixture is treated and worked up asdescribed under instruction (A) (l) (a). 1688 g of a white crystal mass(corresponding to 98.0% of theory) are obtained.

The product can be purified by recrystallisation from acetone. Thepurified substance melts at 7072C.

Elementary analysis shows the following:

3-( 2 -hydroxyethyl )-5 ,5-

The proton-magnetic resonance spectrum also shows, through the agreementof the integration with the number of protons theoretically present,that the substance has the formula given below:

H- N N- CH Gri -:01;

3. Manufacture of dimethylhydantoin.

256.3 g of 5,5-dimethylhydantoin (2 mols) and 2.54 g of lithium chloridein 300 ml of dimethylformamidc are stirred at 65C. 158.8 g of 1,2-buteneoxide (22 mols) are slowly added dropwise at this temperature, over thecourse of 2 hours. Thereafter the mixture is stirred for a further 4hours at 100C. The solution is cooled to room temperature and filtered,and the filtrate is then concentrated at C/20 mm Hg on a rotaryevaporator and dried to constant weight at C/0.l mm Hg. A crystalline,light yellow crude product is obtained in quantitative yield (400.1 g).The substance can be purified by recrystallisation from acetone.Colourless, glistening crystals which melt at 8788.5C are obtained.

Elementary analysis shows the following:

3-( 2 '-hydroxy-n-butyl )-5 ,5

Found: Calculated:

4. 3'(2-Hydroxypropyl)-5,5-dimethyl-6-isopropyl-5,6- dihydrouracil.

A suspension of 276.5 g of 5,5-dimethyl-6- isopropyldihydrouracil 1.5mols), 10 g oflithium chloride and 1750 m1 of dimethylformamide isstirred at 50C. 116.2 g of propene oxide (2.0 mols) are added dropwisethereto over the course of 210 minutes whilst stirring. The temperatureis at the same time raised to 62C, and the suspension changes to aclear, colourless solution. After the addition, the mixture is stirredfor a further 12 hours at 8688C. After cooling, the pH is adjusted to7.0 (with a little strength sulphuric acid), and the mixture isfiltered, completely concentrated at 120C under a waterpump vacuum andsubsequently dried to constant weight at 120C under 0.2 mm Hg.

An ochre-coloured, clear, slightly tacky, brittle substance is obtainedin 95% yield (345 g); its analysis by combustion shows that the crudeproduct obtained is the desired compound.

Calculated for hydroxy- Calculated for dimethylhydantoin.

A solution of 508 g of 5,5-dimethylhydantoin (3.96 mols) and 5 g oflithium chloride in 550 ml of dimethylformamide is stirred at l-130C.

534 g of 90% strength styrene oxide (4.00 mols) are added dropwise tothis clear solution over the course of 90 minutes, whilst stirring.Thereafter the mixture is stirred for a further 4 hours at 120C. Aftercooling to 25C, the mixture is filtered, and the colourless, clearsolution is concentrated at 80C on a rotary evaporator, under awaterpump vacuum. It is then dried to constant weight at 80C under 0.15mm Hg. The crude product, which is obtained quantitatively, isrecrystallised, without further characterisation, from 2.5 litres ofacetone. 646.3 g (65.8% of theory) of colourless fine crystals, meltingat 146146.4C, are then obtained (without working up the mother liquor).Analysis by combustion shows that the desired product has been obtained.

Found Calculated 62.86% C 62.89% C 6.407! H 6.509: H 11.55% N 11.28% NFurthermore, the IR and NMR spectra are in agreement with the expectedstructure. The mass spectrum also shows that the structure given belowis correct. The molecule-ion is detected at 248 MU (mass units),agreeing with the theoretical molecular weight o1- 238.3. Furthermore,the following fragments are found: 231 MU 248-OH); 171 MU (=248-C H 142MU 248-C H CHO), 127 MU l24-C 3) etc.

H 0 CH 0 H-N N-CH -C"OH 6. Manufacture of 3-(2-hydroxy-n-propyI)-5,5-

pentamethylenehydantoin.

An amount of 1514 g of 5,5- pentamethylenehydantoin (9 moles) is stirredtogether with 33.6 g of potassium chloride and 3.6 litres ofdimethylformamide at 60C. There is then made to this thin suspension,within 2 hours, a dropwise addition of 575 g of propene oxide (9.9moles); the temperature is raised during this operation to C. After thepropene oxide addition, the temperature is raised within 6 hours to100C; a clear solution is thus formed. After hot filtration, thesolution is concentrated to dryness in a water-jet vacuum at 70C. Theresulting product is dried at C under 0.3 Torr to constant weight. Thereis obtained an amount of 2005 g (98.6%) of a colourless to slightlyyellowish crystalline mass, which melts at 157.7C. (Mettler FP, 2C/min).

The product can be purified by recrystallisation from methanol.

The thus produced alcohol corresponds to the following formula:

H-N 2 I l CH B. Diesters mediately. After minutes, 15.5 ml of water haveseparated (86.1% of theory). After a total of 3.5 hours, 17 m1 of waterhave separated (94.5% of theory), and the condensation is completed.

The mixture is cooled to 25C, treated with 200 ml of toluene, andextracted by shaking with 70 ml of wa ter; the wash water is immediatelyseparated off and the organic phase is cooled to 10C. Hereupon thediester crystallises out. After drying (60C/2O mm Hg), 230 g of thecrude diester (90.2% yield) are obtained. The binueleardimethylhydantoin derivative obtained can be purified byrecrystallisation from acetone. The purified product consists ofcolourless crystals which melt at 8889C.

The infrared spectrum shows, through the absence of the OH absorptionand the presence of the estercarbonyl vibrations in addition to thecarbonyl frequencies originating from the hydantoin ring, that theproduct corresponds to the formula given below:

sence of the OH frequencies of the alcohol; the absorptions to beallocated to the ester-carbonyl and hydantoin-earbonyl groups are at1715 cm, l740 cm and l8l5 cm.

Elementary analysis shows that the material contains 12.9% N(calculated, 13.1%).

The proton-magnetic resonance spectrum (60 Me H-NMR, recorded indeuterochloroform at 37C. with tetramethylsilane as the internalstandard) also shows, through the presence of the following signals,that the binuclear dimethylhydantoin derivative obtained possesses thestructure given below:

H3 CH3 H. C-(i 1-C=O i 3 ('3 CH3 H-N\ i -CH CH -O- -(CH2)8- O-CH2CH2-N/\l-H e11 l2 protons: 6 1,45 (singlet): twice 0 I g p u 4 protons: 62.60 (singlet): -CI -CI I -C- 8 protons: 6 5.7 309 (two triplets): twicea 4.20-4.40 0' N C" CH O\C r: I- I- a I 2 protons: 6 6.60 (ill-definedsinglet): twice Z 26 protons 2. Manufacture of the diester from 1 mol ofsuccinic acid and 2 mols of 3-(2-hydroXyethyl)-5,5- dimethylhydantoin.

l72 g of 3-(2'-hydroxyethyl)-5,5-dimethylhydantoin (1 mol) are condensedas described under instruction (B) (l), with 59 g of succinic acid (0.5mol), with the addition of l70 ml of toluene and 3.0 ml of concentratedsulphuric acid, over the course of 3 hours at ll C.

On cooling to room temperature, the product crystallises out directlyfrom the reaction mixture.

For purification, the crystalline mass is recrystallised from 1500 ml ofacetone. 163.2 g of purified product (77% of theory), melting at l47l48C, are obtained.

The infrared spectrum (Nujol paste) shows the ab- 3. Manufacture of thediester from 1 mol of sebacie acid and 2 mols of3-(2'-hydroxy-n-propyl)5,5- dimethylhydantoin.

690 g of 3-(2'-hydroxy-n-propyl)-5,5- dimethylhydantoin (3.7] mols) arecondensed with 375.2 g of sebacie acid L mols) in accordance with theinstruction under (B) (l). 500 ml of toluene are used for the azeotropicremoval of water; 10 ml of concentrated sulphuric acid are added as thecatalyst. The condensation is carried out in 15 hours at l l0-l l8C;63.0 ml of water have then been removed of theory). The reaction mixtureis cooled to 35C, treated with 500 ml of toluene and twice washed withml of water. Thereafter the organic phase is concentrated at 60C on arotary evaporator, under a waterpump 3 ,872,097 17 18 vacuum. T pr u iSq n ly dried Constant 5. Manufacture of the diester from 1 mol of adipicacid weight at 80C/O.l mm Hg. 929 g of a clear, transpard 2 mol of3-(2-hydmxy-n-butyl)-5,5- ent, light yellow, highly viscous product(92.9% of thedi th lh dantoin,

ory) are obtained, essentially consisting of the com- 142 g of3-(2-hydroxy-n-butyl)-5 5 Pound of the followmg Structure: 5dimethylhydantoin (0.7l mol) are condensed with 5 1.8

(3H 0 Q CH H C CH 5 3 (i O= C- C CH v N\ /l\-CH I O- -(CH -.-O- |-CH -N)tL-H.

H H I 4. Manufacture of the diester from 1 mol of sebacic g of adipicacid (0.355 mol), with the aid of 142 ml of acid and 2 mols of3-(2'-hydr0Xy-n-butyl)-5,5- toluene and 3.6 g of concentrated sulphuricacid, analdimethylhydantoin. ogously to the instruction under B. 4.,over the course 200 g of 3-(2'-hydroxy-n-butyl)-5,5- of 10 hours atl06l08C. 12.2 ml of water are sepadimethylhydantoin (1 mol), 101 g ofsebacic acid (0.5 rated off during this time (95.3% of theory). Workingmol), 3 ml of concentrated sulphuric acid and 170 ml up takes placeaccording to instruction (B) (4), and

of toluene are mixed and condensed over the course of 167 g of a clear,transparent, slightly yellowish, highly 12 hou s at in accordance withthe viscous product are obtained, of which the infrared struction underB. l. The reaction mixture is cooled to Spectrum agrees with the f ll iStructure;

i111 CH H C"- =0 O= -CCH I H O O l n 1 H-N N-CH -C-O-C-(Cn -o-O- -CH -N-11 \C/ H a \C/ A 2 I 2 g 3' 5 room temperature, diluted with 250 ml oftoluene and 6. Manufacture of the diester from 1 mol of glutaricsuccessively eluted with lOO ml of water, 100 ml of 5% acid and 2 molsof 3-(2'-hydroxy-n-propyl)5,5-

strength sodium bicarbonate solution and again with dimethylhydantoin.100 ml of water. The organic phase is first concen- 186 g of3-(2'-hydroxy-n-propyl)-5,5- trated and then dried, on a rotaryevaporator, as dedimethylhydantoin (1 mol) are esterified with 66 g ofscribed Under instruction 269 g of a light y l- 40 glutaric acid (0.5mol) in the presence of 5 g of p-tol- 10W, Clear, transparent, highlyViSCOuS si 5 Of uenesulphonic acid and 150 ml of toluene, as describedtheory) are obtained. under instruction (B) ('4), over the course of 12hours Elementary analysis ShO S 59.1 and at l 15C. After working up inaccordance with instruc- (ealculaledl 593%, 3.2%, d 9 N)- tion B. 4., asolid, amber-coloured product l 50 g, cor- The infrared spectrum furthershows, through the abresponding to 64% of theory) is obtained, whichessensence of OH frequencies and through the presence of tially consistsof the compound of the following forthe ester-carbonyl absorptions, thatthe product obmula:

a ti CH5 tained essentially consists of the compound of the fol- 7. 148g of the 3-(2-hydroxy-2-phenyl-ethyl)-5,5- lowing structure:dimethylhydantoin manufactured according to Exam- 2 ii (:3 H

19 ple (A) (0.596 mol) together with 60.3 g of sebacic acid (0.298 mol),0.8 ml of concentrated sulphuric acid and 200 ml of toluene aresubjected to an azeotropic circulatory distillation, whilst stirring.Whilst doing so,

with 125.2 g of sebacic acid, 400 ml of toluene and 9.5 ml ofconcentrated sulphuric acid are subjected to an azeotropic circulatorydistillation whilst stirring, the bath temperature being 170C and thereaction temthe bath temperature is 192194C and the reaction 5 perature116C. The period of reaction is 24 hours, in temperature is 115C. Thewater which has been disthe course of which a further 7 ml ofconcentrated sultilled off azeotropically is separated off and removed.phuric acid are added. A further 2.5 ml of sulphuric acid are added insmall 20.5 ml of water separate (91% of theory). Working portions overthe course of 24 hours. After the indiup takes place according toExample (B) (7). 346 g of cated time, 10.7 ml of water have beenseparated off the light brown, clear, viscous diester (85.8% of the-(100% of theory). The reaction mixture is then cooled ory) are obtained.to 0C, whereupon a little unreacted starting product 9. A mixture of 894g of 3(2-hydroxy-n-propyl)-5,5- precipitates (melting point 130C). Theclear filtrate is dimethylhydantoin (4.80 mols), 302.5 g of 71.4?! twiceextracted be shaking with ml of water, sepastrength oxalic acid (2.40mols), 750 ml of benzene rated off and concentrated to dryness at -70C15 and 5 ml of 50% strength phosphoric acid is distilled under awaterpump vacuum, on a rotar evaporator I azeotropically for 40 hours at140C bath temperature is then dried to constant weight at C under 0.2 mmand l i n mp r r hil irring, in H the manner described in Example (B)(7). Over the 1433 g (725% f h f a glassy i l course of this period, afurther 40 ml of 50% strength stance, which softens at 3540C, areobtained. 20 Phosphoric acid are added- 190 ml of water 1 Elementaryanalysis shows that the desired diester of (97% of y) The resulting fslurry h Structure given below has been produced cooled to roomtemperature and diluted with 500 ml of ethyl acetate, and the thinsuspension is twice washed with 200 ml of water. Thereafter, the newdiester is iso 25 lated by filtration. After drying, 231 g of a finecolour- Found Calcu'med less powder melting at 212.4C are obtained.Analysis of the crude product by combustion shows a nitrogen H H contentof 12.9% (calculated 13.1%); the new diester N N corresponds to thefollowing formula:

0\ H 0 CH3 0 0 I l i ll ll 1 11-11 N-cH -c 10o(cH)c-0-cHcn N-H' H O CH 0s v 0 14 i! 3 0 0 ll 11 H-HVW'-CH 13H'Q C C-O"TH-CH N NH ll 0 CH-3 OH3 I(I;

8. 300 g of the 3-(2'-hydroxy-n-propyl)-5,5- 10. Diester from sebacicacid and 3-(2-hydroxy-ndimethyl-6-isopropyl-5,6-dihydrouracilmanufactured according to Example (A) (4) (1.24 mols) togetherpropyl)-5,5-pentamethylene-hydantoinv An amount of 1245 g (5.5 moles) of3-(2-hydroxy-n- 21 22 P PY 'P y y manufactured through a column andremoved from the apparatus. according to instruction A 6 are esterifiedwith 2 The xylene is separated from the methanol by extracg moles)Sebacic acid in litres of toluene tion by shaking with water and, afterdrying, fed back uhdel' the catalytic effect of 50 ml of 50% sulphohlcto the reaction mixture. The diester formation is comuCid, as describedin insh'uclioh After 8 hours, pleted in this manner in about 48 hours.All volatile the Separation of water is Complete-The Warm Solutionconstituents are then distilled off at 190C under is washed With l 0 10of Sodium hy xi Torr, and the crude product, obtained in quantitativelution, till it i neut a t i is Washed with 1 litre of yield, isolated.This is purified by recrystallisation from water. After separation, thesolution is concentrated to a mixture f di th lf mamide and water (4;1 5ml dryness and then subsequen ly dries at of solvent being used to l gof substance. There is thus to constant weight. There is thus obtainedan amount obt ined from the above charge 1068.5 g (correspondof 1414 g(96 of theory) of the desired diester. The ing to 53.2% of theory) ofthe pure diester, M.P. crude product melts at l-l58C (Mettler FP 51:263,1"C (Mettler PF 51, 1C/min) in the form of coi The Crude i t r Can epurified by recryslourless fine crystals. The elementary analysis showstallisation from choroform/acetone. The proton- 15 the following:magnetic resonance spectrum Mc-HNMR) shows that the product correspondsto the formula given be- Fomd Calcumed low: 57.5 72 c 57.4 c

O O O O H 1-c iioiiacliioiictiivh l 1. Diester from trimethyladipic acid(isomer mixture) H H 30 11.2%N 11.2%N and 3-(2-hydroxy-n-propyl)-5,5-dimethylhydantom.

An amount of 1130 g of trimethyladipic acid (commercial mixture ofisomers) (6.0 moles) is heated together with 1.5 litres of toluene and2456 g of 3-(2'- And likewise the spectroscopical findings are inhydroxy-n-propyl)-5,S-dimethylhydantoin (13.2 agreement with thefollowing structure:

e 0 79' @t t moles), and the mixture, under the catalytic effect of 13.Diester from isophthalic acid and 3-(2'-hydroxy-n- 100 ml of 50%sulphuric acid, and with stirringand azepropyl)-5,S-dimethylhydantoin.otropic circulatory water distillation, esterified, the In an analogousmanner to that of (12), the correprocess taking about 30 hours.Additions are then spending isophthalic acid ester is produced by thereacmade of80gof active charcoal and 50 gof Aerosil,and 50 tion of 194.2g of isophthalic acid dimethyl ester (l stirring continues for 30minutes at C. The solution mole) with 372.4 g of3-(2-hydroxyn-propyl)-5,5-

is then filtered clear, diluted with 2 litres ofchloroform,dimethylhydantoin (2 moles) in 700 ml of xylene, in and then washed oncewith 500 ml of 10% sodium hythe presence of 2 g of lead-ll-oxide, 2 gofantimonousdroxide solution and twice with 1 litre of water eachIll-oxide and 2 g of tetraisopropyl-ortho-titanate. The

time. After separation, the solution is concentrated at 55 processingprocedure is carried out according to (12). 70C in a water-jet vacuum,and subsequently dried at There is then obtained 489 g (98.3% of theory)of C/0.3 Torr to constant weight. There is thus obcrude product, whichis purified by recrystallisation tained an amount of 2258 g (71.7%oftheory) of the from ethyl acetate to obtain 234.3 g (46.6% of theory)desired diester in the form of a highly viscous, clear, of colourlesscrystals melting at 202205C. The elelight-brown substance. 60 mentaryanalysis gives the following results: 12. Diester from terephthalic acidand 3-(2'-hydroxyn-propyl)-5,5-dimethylhydantoin.

A mixture of 776 g of dimethylterephthalate (4 moles), 1488 g of thealcohol used in 11.) (8 moles),

2 1 of xylene, 6 g of lead-ll-oxide, 7 g of tetraiso- 65 Gunpropylorthotitanatc and 6.5g of antimonous-lll-oxide 57.1 71 c 57.4 /1 cis caused to react at C. During the reaction, the az- 8 a 2; g

eotrope from methanol and xylene is distilled off -.O-C-C -H 14. Diesterfrom hexahydrophthalic acid and 3-(2- 441.3 g (87.9% of theory) of asolid mass of which the hydroxy-n-propyl)-5,5-dimethylhydantoin.

There is obtained, by esterification of 115.5 g of hexahydrophthalicacid anhydride (1.5 moles) with 280 g of 3-(2-hydr0xyn-propyl)-5,5-

dimethylhydantoin (0.75 mole) in 250 ml of toluene,

with 15 g of cone. sulphuric acid as catalyst, a lightbrown, clearreaction mixture, from which are removed by circulatory waterdistillation, within 20 hours, 13.50 ml of water (100% of theory). Theprocessing procedure is according to (11). There is thus obtained anamount of 332.4 g (87.3% of theory) of a clear, resinlike, light-brownsubstance corresponding to the following formula:

C. ac. 0-

melting point is 6769C, and which consists of the crude diester.

16. Diester from adipic acid and3-(2-hydroxy-npropyl)-5,5-dimethylhydantoin.

An amount of 292.3 g of adipic acid (2 moles) is estcrified, in themanner described under (1 1), with 744 g of3-(2-hydroxy-n-propyl)-5,5-dimethylhydantoin (4 moles) in 600 ml oftoluene, in the presence of 20 g of cone. sulphuric acid, the operationtaking 7 hours. After processing analogously to 1 1 a light-coloured,clear, highly viscous substance to the amount of 964 g (100% of theory)is obtained, which slowly crystallises out. For purification, a part ofthe substance is recrys- C TI tallised from dioxane. Colourless crystalsare obtained which melt at 151.3C (Mettler PF 51; 2C/min). The

elementary analysis gives the following results:

Found Calculated 54.6 "/1 54.7 "/1 C 7.0 H 7.1 "/1 H 11.3%N 11.671N

The H-NMR-spectrum is in agreement with the following structure:

EXAMPLE 1 A mixture of 929.0 g 1.725 mols) of the diester from t GH-CH-CH -N\?/ 2 1 mol of sebacic acid and 2 mols of3-(2'-hydroxy-npropyl)-5,5-dimethylhydantoin, manufactured accord ing toinstruction (B) (3), 3200 g of epichlorohydrin (34.5 mols) and l 1.3 gofa 50% strength aqueous solution of tetramethylammonium chloride iswarmed to 60C, whilst stirring. Thereafter, an azeotropic circulatorydistillation is started at 60C and 60-80 mm Hg. 332 g of 50% strengthaqueous sodium hydroxide solution (4.15 mols) are then added dropwiseunder these conditions over the course of 60 minutes, with vigorousstirring; at the same time water present in the reaction mixture iscontinuously removed from the system and separated off. After completionof the addition of the sodium hydroxide solution, distillation iscontinued for a further minutes in order to remove the residual water ascompletely as possible. In total, 220 ml of water are separated off(96.5% of theory).

The mixture is now cooled to C and the sodium chloride produced in thereaction is removed by filtration. The sodium chloride precipitate isrinsed with 150 ml of epichlorohydrin. The combined epichlorohydrinsolutions are extracted by shaking with 200 ml of water. The organiclayer is then completely concentrated at 70C on a rotary evaporator,under a waterpump at 8590C under 0.1 mm Hg. 1041 g (93% of theory) ofaclear, transparent, pale amber-coloured, highly viscous epoxide resinare obtained. The epoxide content is 3.06 equivalents/kg (99% oftheory). The total chlorine content is 0.5%. The new epoxide resinessentially consists of the compound of the following structure:

0H iv on 05011 EXAMPLE 2 240 g (0.4238 mol) of the diester, manufacturedaccording to instruction (B) (4), from 1 mol of sebacic acid and 2 molsof 3-(2-hydroxybutyl)-5,5- dimethylhydantoin, together with 1 176 g ofcpichlorohydrin (12.72 mols) and 2.105 g of tetraethylammonium chloride(3 mol percent) are stirred for 60 minutes at l l6l 17C. A pale yellowclear solution is thereby produced. An azeotropic circulatorydistillation is then started at 60C, as described in Example 1, and 84.8g of strength aqueous sodium hydroxide solution are added dropwise overthe course of 60 minutes. The procedure mentioned in Example 1 isfollowed, and the mixture is worked up in accordance with Example 1. 276g of a pale yellow, clear, transparent, highly viscous epoxide resin(96.1% of theory) are obtained, having an epoxide content of 3.0 equiva'lents/kg and a total chlorine content of 0.8%.

The proton-magnetic resonance spectrum (60 McHNMR, recorded in CDC] at37C, with tetramethylsilane as the internal standard) shows inter aliathrough the presence of the following signals, that the new epoxideresin essentially consists of the compound vacuum, and is subsequentlydried to constant weight 40 of the following structure:

0.95 (tri let, J 6. 5 Hz) twice -CH2-CI 5 1.05

- 5 s 1,2 4.70 (multi let) twice 0 -(ct I t twice -C-C2--CH3 2.22 (trilet, J 6.. 5 Hz) twice -0-0-c 5 -cn 0 2.55-2.90 (septet) twice 05 -03-006 3.08 (multiplet) twice CHTQWWZ 30 -410 (multipleb) 2 4 x EXAMPLE 3 CCH 1, and 52.9 g of 50% strength aqueous sodium hydroxide solution(0.331 mol) are added dropwise over the 40 course of 60 minutes, withvigorous stirring. During this operation, and during the subsequentworking up, the procedure according to Example 1 is followed.

The new epoxide resin, which has an epoxide content 50% strength aqueoussodium hydroxide solution over the course of 1 hour at 60C, whilststirring vigorously and continuously separating off water. The mixtureis worked up in accordance with Example 1. 150.2 g of a clear, viscousepoxide resin (89.7% of theory) are obtained, having an epoxide contentof 3.45 equivalents/kg (100% of theory) and a total chlorine content Theproton-magnetic resonance spectrum shows that the end product has thefollowing structure:

EXAMPLE 113.9 g (0.2673 mol) of the diester, manufactured according toinstruction (B) (2), from 1 mol of succinic acid and 2 mols of3-(2-hydroxyethyl)-5,5

of 3.09 equivalents/kg (96% of theory) and a totaldimethylhydantoin,together with 741 gofepichlorohychlorine content of0.8%, is obtained in 81% yield (133.5 g).

The new epoxide resin essentially corresponds to the compound of thefollowing structure:

drin and 1.3 g of tetraethylammonium chloride, are stirred for 60minutes under reflux at 116-118C. Thereafter the product isdehydrohalogenated with 53.4 g of strength sodium hydroxide solution, in

3 3 11 o c- =0 0= e-ea 0 5 3 or C C- l 1 1 T A 11- H /N-CH CH -O- -(CH-O-CH --CH -N /l\.-CH -CH-0H EXAMPLE 4 135 g (0.2885 mol) of thediester, manufactured according to instruction (B) (6), from 1 mol ofglutaric acid and 2 mols of 3-(2-hydroxy-n-propyl)-5,5-dimethylhydantoin, 1329 g of epichlorohydrin (14.36 mols) and 2.4 g oftetraethylammonium chloride are mixed, and the mixture is stirred for120 minutes at 100C. This clear solution is dehydrohalogenated, asdescribed in more detail in Example 1, with 95,8 g of accordance withExample 1, for one hour at C, whilst stirring vigorously andcontinuously removing water from the system. The product is worked upanalogously to Example 1, and 141 g (98.3% of theory) of a clear,transparent, practically colourless, highly viscous epoxide resin areobtained, having an epoxide (3'5 i s H C -C '-C=0 v O=C C "CH 1 i CH--CH--CH -N I-l-CH -CH -O --CH -CH -C --CH -Q?H -N\ /N-C1l -Cq-}3H \tlfi I O EXAMPLE 6 (145 g). The NMR spectrum essentially agrees with the Asolution of 126 g of the diester manufactured acfollowing structure:

H C CH O O TLC CH 3 3 9 3 L I i "o Q l l o i: (CH t o i a ca '06 bit HC-Cl-l-CH N\C/N CH CH 2 8 CH CH N\c/ 2 ll 4 1| 0 10 cording to Example(B) (7) (0.19 mol), 1.3 g of 50% EXAMPLE 7 strength aqueoustetramethylammonium chloride and 740 g of epichlorohydrin (8.0 mols) isStirred for 45 161.4 g of the diester manufactured according toExminutes at 60C. An azeotropic circulatory distillation ample (B) (3)(03 mol) together f g of 50% is then 50 adjusted, by applying a vacuummm strength aqueous tetraethylammonium chloride and Hg) at 140C bathtemperature, that the temperature 639 g of B-mcthylepichlomhydrin (60mols) are i h reaction fl k i 59 6()C stirred for minutes at 60C,analogously to Example 36.5 g of strength aqueous sodium hydroxide so- 36. The product is then dehydrohalogenated with 57.7 lution are thenadded dropwise over the course of 100 g of 50 strength aqueous sodiumhydroxide solution minutes, with vigorous stirring; at the same time the(0.722 mol), in accordance with Example 6. Working water present in thereaction mixture is continuously up is also effected exactly inaccordance with Example distilled off azeotropically and separated off.After 6. completion of the addition of the sodium hydroxide so- 40 168 gof a light yellow, clear epoxide resin (82.6% of lution, circulatorydistillation is continued for a further theory) are obtained. Theepoxide content is 3.07 ep- 30 minutes. oxide equivalents/kg and thetotal chlorine content is Thereafter the mixture is cooled to 40C andthe soless than 0.3%. The new epoxide resin essentially corrediumchloride produced during the reaction is removed sponds to the followingstructure:

0 CH 0 o H (1 ca 5 3 5 C-- I 0 0 0 i o H c c CH I I n N-Cli c ca m 2 I 2t CH its 0 c (cs c 0 lat-i CH tt c/ 2 2 CH CH 3 H CH 31-1 ll 3 byfiltration. The epichlorohydrin solution is twice ex- I EXAMPLE 8tracted by shaking with 50 ml of water, in order to remove remnants ofsodium hydroxide and of sodium chloride. After separating off theaqueous phase, the solution is concentrated to dryness at C on a rotary6O evaporator, under a 'P l p vacuum; 50 ml of 60C, in accordance withExample 6. The product is water are then added and distilled off.Thereafter, the then dehydrohalogenated with 934 g f 50% strength tracesof water are removed by adding 50 ml of toluene aqugous di h d id l i 123 l as d and distilling off azeotropically. The product is then ib d iE l 6,

dried to constant weight at 60C under 0.2 mm Hg (4 After working upaccording to Example 6, 386 g of hours). A clear, pale yellowish,viscous epoxide resin aclear, light ochre-coloured epoxide resin (98%otthewith 2.9 epoxide equivalents/kg, having a total chlorine ory) areobtained, having an epoxide content of 1.8 epcontent of less than 0.371,isobtained in 98.4% yield oxide equivalents/kg (68.7% of theory).

333 g of the diester manufactured according to Example (B) (8) (0.512mol) are stirred with 1000 g of epichlorohydrin (10.8 mols) and 3.40 gof 50% strength aqueous tetramethylammonium chloride at EXAMPLE 9 Amixture of 192 g of the bis-oxalate ester manufactured according toExample (B) (9) (0.45 mol) with theory) of a light-yellow viscousepoxide resin having an epoxide content of 3.07 equivalents/kg. Thetotal chlorine content is 0.7%. The new sebacic acid-di-(lglycidyl-S,5-pentamethylenchydantoin-3-yl-propyl- 1760 g ofepichlorohydrin (19 mols) and 3 g of 50% 5 (2))-estcr corresponds to thefollowing structure:

h 0 CH strength aqueous tetramethylammonium chloride solu tion is warmedfor 1 hour to 90C whilst stirring, analogously to Example 6. The thicksuspension is then dehydrohalogenated with 86.4 g of 50% strengthaqueous sodium hydroxide solution (1.08 mols) in accordance with Example6. The reaction is incomplete, since the starting product is onlypartially dissolved in the reaction medium.

The mixture is nevertheless worked up in accordance with Example 6, and86 g of an epoxide resin (36% of theory) are obtained, containing 1.95epoxide equivalents/kg (52% of theory).

EXAMPLE l0 Additions of 3870 g of epichlorohydrin (41,8 moles) and 11.9g of 50% aqueous tetramethylammonium chloride solution are made, exactlyin the manner described in the manufacture example 1, to l 116 g of thediester (1.8 moles) produced according to (10), the whole being thenreacted. Dehydrohalogenation is carried out with 347.5 g of 50% sodiumhydroxide solu tion, with this and the following procedure beingperformed according to Example 1.

There is obtained an amount of 1124 g (85.2% of EXAMPLE 11 An amount of1049 g of the diester (2 moles) produced according to (1 1 is reacted,exactly analogously to Example 1, with 3700 g of epichlorohydrin (40moles) under the action of 13 g of 50% aqueous tetramethylammoniumchloride, and with 368 g of 50% aqueous sodium hydroxide solution (4.6moles) for dehydrohalogenation. The processing of the charge and theisolation of the product are effected likewise according to Example 1.There is obtained an amount of 1050 g of a clear, brown, viscous resin(82.5% of theory), the epoxide content of which is 3.25 equivalents/kg.The total chlorine content is below 0.3%. 0.1% being hydrolysablechlorine and 0.023% ionogenic chlorine. The elementary analysis givesthe following results:

Found Calculated 58.40 C 58.47 71 C 7.60 71 H 7.60 7l H The new epoxideresin corresponds essentially to the following structure:

EXAMPLE 12 chlorine content is 0.5%. The crude product can be purifledby recrystallisation from acetone. Colourless crystals are then obtainedwhich melt at 140.2C (Mettler PF 51, 2C/min) and which have an epoxidecontent of 3.26 epoxide equivalents l% of theory). The

elementary analysis and the 60 Mc H-NMR-spectrum show that the productcorresponds to the following formula:

H O O H I II H e- 9 i mole) produced according to (I3) is reacted,exactly in the manner described in Example 1, with 841 g ofepichlorohydrin (9.05 moles), 3.0 g of aqueous tctramethylammoniumchloride and 87.3 g of 50% aqueous sodium hydroxide solutions 1.09moles), and then processed likewise as described in the said example.There is obtained 268 g (96.4% of theory) of a light-yellow, highlyviscous resin having 3.7 epoxide equivalents/kg and a chlorine contentof 1.4%. The new epoxide resin corresponds essentially to the followingformula:

EXAMPLE 14 An amount of 203 g of the diester (0.4 mole) producedaccording to (l4) is glycidylated according to Example 1, withapplication of the following reactants:

1110 g of epichlorohydrin (12 moles) 2 g of tetraethylammonium chloride,anhydrous,

77 g of 50% aqueous sodium hydroxide solution (0.963 mole) Theprocessing and isolation of the product are effected likewise accordingto Example 1, with the aid of 250 ml of epichlorohydrin for subsequentwashing and 180 ml of water for extraction of the solution.

There is obtained an amount of 213 g of a highly viscous, resin-likediepoxide (86% of theory), the epoxide content of which is 3.05equivalents/kg (94.4% of the- EXAMPLE 13 An amount of 227 g of thepurified diester (0.452

ory); the total chlorine content is 1.2%. The new epoxide resin has thefollowing structure:

35 36 EXAMPLE l USE EXAMPLES The following are reacted according toExample 1: 94 g of dicster. produced according to (0.17 mole). 346 g ofepiclilorohydrin (3.74 moles) 0.9 g of tetruethylammonium chloride.anhydrous. 30 g of 50% aqueous sodium hydroxide solution.

The processing after the reaction is carried out analoa. Amine CuringReactions gously to that described in Example 1, and the followingproduct is isolated: 10 bXAMPLE I An amount of 80 g (69.6% of theory) ofa viscous 75 parts'ofthe epoxide resin manufactured according resinhaving 3.12 epoxide equivalents (kg) (95.7% of to Example 1, containing3.06 epoxide equivalents/kg, theory). The total chlorine content is0.5%. The epoxare mixed with parts of 1,4-butanediol-diglycidylide resinhas, according to NHR, essentially the followether as a reactive diluentand with 20 parts of triethyling structure: enetetramine, at roomtemperature, and the mixture is EXAMPLE l6 poured into casting mouldsmade of aluminium. Curing An amount of 798 g of the (ester (L66 moles)takes place for 48 hours at room temperature. The retrained according to(16) is reacted in the manner sultmg mouldings possess the propertiesindicated bescribed in Example l with 3085 g of epichlorohydrin low:(33.4 moles), 10.9 g of 50% aqueous tetramethylammonium chloride and318.5 g of 50% aqueous so- Flexuml Strength VSM 7mm 2-3 Kp/mm (no diumhydroxide solution (3.98 moles). After the usual Fracture at processing(cp. Example 1, etc.), 895.1 g 91.0% of maximum deflect) theory) of aclear, pale yellowish, viscous epoxide resin D fl i VSM 77,103 mm isobtained, the epoxide content of this being 3.54 equivalents/kg and thetotal chlorine content 0.5%. Impact VSM 77l05 100 cmkplcmz The productcan be purified by recrystallisation from 40 Heat distortion pointaccordmethanol/water (1:1). There is thus obtained a colouring DIN i458RT 0C o L less crystallisate which melts at 106.1 C (Mettler FPiwmerabsmpmm after. dayS 51, 2C/min). The epoxide content is then 3.37equiva- 125C. 60 4 mm test rod y weight lents/kg (l00% of theory). Theelementary analysis gives the following results:

EXAMPLE 11 Found Calculated 65 parts ofthe epoxide resin manufacturedaccording to Example 1, containing 3.06 epoxide equivalents/kg, 56 3 C56.5 c are mixed with 35 parts of the diglycidyl-ether of 3; Z S Z: g A-cyclohexene-dimethanol-l,l as a reactive diluent 1655 than 0 3 chiorchmine and 30 parts of a medium-viscosity adduct curing agent containingamine groups (manufactured by warming a 7 mixture of 77 parts of amedium-viscosity diomethane- The mass spectrum shows, with themolecule-ion depolyglycidyl-ether resin having an epoxide content oftected at 594 mass units (molecular weight theory approx. 5.0equivalents/kg and a viscosity of 594), and by characteristicfragmentations, that the del3,000l 6,000 cP, and of 158 parts oftechnical sired product has been obtained; this is confirmed alsotrimethylhexamethyleneamine, and subsequent addiby the H-NMR-spectrum.tion of 39 parts of phenol), having a H -content H3 CH 9 2 -c- 0 O -CH4? 3 i..- t5 3 it...

67, at room temperature, and the mixture is poured into casting mouldsmade of aluminium. Curing took place over the course of 48 hours at roomtemperature. The resulting mouldings have the following properties:

Flexural strength, VSM 77,103 1-2 kp/mm (no fracture at maximumdeflection) Deflection, VSM 77,103 20 mm Impact strength, VSM 77,105 100cmkp/cm Heat distortion point according to Martens, DIN 53,458 RT CWater absorption after 4 days at 25C (60X10X4 mm test rod) 0.8-1.2 percent by weight Water absorption after 1 hour at 100C (60 10X4 mm testrod) 1-2 per cent by weight EXAMPLE III Flexural strength, VSM 77,103Deflection, VSM 77,103 Impact strength, VSM 77,105 Boiling waterabsorption 1 hour) 9.1 kp/mm 6.4 mm 37.5 cmkp/cm EXAMPLE IV 80 g of theepoxide resin manufactured according to Example 3, containing 3.09equivalents/kg, are mixed In the following comparison test it is shownthat certain mechanical properties, especially the impact strength, ofthe casting obtained by curing the epoxide resin according to Example111 are better than those of the casting obtained by executing Example Iof the US. Pat. No. 3,542,803:

A mixture of 211 g of 1,l2-bis(5',5'- dimethylhydantoinyl-3')-dodecane(0.5 mol), 1387,5 g of epichlorhydrin mols) and 0.5 g oftetramethylammonium chloride was heated to 1 17C for 5 hours. A resinsample contained 1.3 epoxide equivalents/kg. 45.36 g of 97% strengthsodium hydroxide were added in portions to the solution cooled to 60Cover the course of 35 minutes. The temperature was kept at 60C by slightcooling. After addition of the sodium hydroxide the mixture was stirredfor a further 30 minutes at 60C. The reaction mixture was thenconcentrated in a vacuum of 35 mm Hg until the entire quantity of thewater of reaction had been distilled off azeotropically. Thereafter thesodium chloride which had formed was filtered off and washed with alittle epichlorhydrin. The reaction product was then furtherconcentrated, firstly at a vacuum of 30 mm Hg in order to recover theexcess epichlorhydrin and finally in a high vacuum. 266 g of1,12-bis-(N-glycidyl-5,5'- dimethyl-hydantoinyl-3)-didecane (99,5% oftheory) were obtained. The light brown viscous resin contained 1.0% ofchlorine and 3,86 epoxide equivalents/kg and had a viscosity of 12,000cp at 20C. 100 parts of this compound were mixed with 9 parts oftriethylene tetramine. The resin-curing agent mixture had a pot life of3000 cp. of 40 minutes at 40C. The resin-curing agent mixture was castinto prewarmed aluminium moulds (4 mm thick sheets for mechanicalmeasurements) and cured for 24 hours at 40C and then for 6 hours at 100Cto give castings. The castings had the following properties:

Flcxural strength according to VSM 77,103: (1.5 kg/mm no fracture onmaximum deflection,

Deflection according to VSM 77,103: 20 mm Impact strength according toVSM 77,105: 23,4 cmkg/cm" Heat distortion point according to Martens(DIN): 34C.

EXAMPLE IV 80 g of the epoxide resin manufactured according to Example3, containing 3.09 epoxide equivalents/kg, are mixed with 6.4 g oftriethylenetetramine at 40C. The homogeneous, clear mixture is cured inan aluminium mould for 24 hours at 4045C. A moulding having thefollowing properties is obtained:

Flexural strength, VSM 77,103

1-2 kp/mm no fracture at maximum deflection 20.0 mm

33-36 cmkg/cin Deflection, VSM 77,103 Impact strength, VSM 77,105 Coldwater absorption, 4 days at 20C b. Curing with Anhydrides.

EXAMPLE V 68.6 g of the epoxide resin manufactured according to Example4 (3.45 epoxide equivalents/kg) are mixed with 31.3 g ofhexahydrophthalic anhydride at C to give a clear, homogeneous melt. Thismixture is cured in an aluminium mould for 2 hours at C 13 hours at150C. A casting having the following properties is obtained:

Flexural strength, VSM 77,103 14.15 kp/mm Deflection, VSM 77,103 7-8 mmImpact strength, VSM 77,105 12-14 cmkp/cm Heat distortion pointaccording to Martens, DIN 53,458 71 C Cold water absorption, 4 days atEXAMPLE VI 1 14 g of the epoxide resin manufactured according to Example1, containing 3.06 epoxide equivalents/kg, are mixed with 46 g ofhexahydrophthalic anhydride at 65C and cured in an aluminum mould overthe course of 2 hours at 80C 15 hours at C. The castings thus obtainedhave the following mechanical properties:

Flexural strength, VSM 77,103 12.0 kp/mm Deflection, VSM 77,103 18.0 mmlmpact strength, VSM 77,105 25 cmkg/cm Tensile strength, VSM 77,101 6.7kp/mm" Elongation at break, VSM 77,101 4.4 7:

Cold water absorption, 4 days at

1. A BINCLEAR N-HETEROCYCLIC N,N''-DIGLYCIDYL COMPOUND OF THE FORMULA(2-X1-OXIRAN-2-YL)-CH2-N<(-Z1-CO-N(-CH2-CH(-R1)-OOC(X)(N-1)-COO-CH(-R1)-CH2-N<(-CO-Z1-N(-CH2OXIRAN-2,2-YLIDENE-X1)-CO-))-CO-) WHEREIN X1 ISHYDROGEN OR METHYL, R1 IS HYDROGEN, METHYL, ETHYL, OR PHENYL, X ISALKYLENE OF 1 TO 4 CARBON ATOMS, CYCLOHEXYLENE, OR PHENYLENE, Z1 IS-C(-R'')(-R")- OR -C(-R'')(-R")-C(-R"'')(-R"")WHEREIN R'', R'''',R'''''' AND R'''''''' INDEPENDENTLY OF ONE A ANOTHER ARE HYDROGEN, ALKYLOF 1 TO 4 CARBON ATOMS OR R'' AND R'''' TOGETHER ARE PENTAMETHYLENE ANDN IS 1 OR
 2. 2. A compound as defined in claim 1, wherein X representsan alkylene of 2 to 8 carbon atoms, cyclohexylene or phenylene.
 3. Acompound according to claim 1, of the formula
 4. A compound according toclaim 1, of the formula
 5. A compound according to claim 1 of theformula
 6. A compound according to claim 1 of the formula
 7. A compoundaccording to claim 1 of the formula